Complexes of 2-heptadecylimidazolines



United States Patent '0 COMPLEXES OF Z-HEPTADECYLIMIDAZOLINES John N. Hogsett, Charleston, W. Va., assignor to Union Carbide Corporation, a corporation of New York No Drawing. Application March 11, 1957 Serial N0. 645,013

9 Claims. (Cl. 260-299) This invention relates to complexes of Z-heptadecylimidazolines and to'a process for their preparation.

More particularly, this invention relates to chelates of Hooccm HOOCQH:

vDi(2-heptadecylimidazoline acetic acid) zinc II chloride.

CuHssOaNACl Zll These compositions include the chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group I of the periodic table. Illustrative of such chelates are: di(heptadecylimidazoline acetic acid) sodium sulfate, di(heptadecylimidazoline acetic acid) sodium hypophosphate, di(heptadecylimidazoline acetic acid) silver nitrate, di(heptadecylimidazoline acetic acid) copper sulfate.

The chelates of my invention can also be formed by reacting Z-heptadecylimidazoline with the salts of the metals of group II of the periodic table. such chelates are: diheptadecylimidazoline Zinc nitrate, diheptadecylimidazoline zinc chloride, diheptadecylimidazoline zinc acetate, diheptadecylimidazoline cadmium sulfate, diheptadecylimidazoline cadmium nitrate, diheptadecylimidazoline cadmium chloride, diheptadecylimidazoline mercury sulfate, diheptadecylimidazoline mercury acetate, and diheptadecylimidazoline mercury bromide. My chelates also include those formed by reacting the acid salts of 2-heptadecylimidazoline with the salts of the metals of group II of the periodic table. Illustrative of such chelates are: di(heptadecylimidazoline acetic acid) magnesium chloride, diheptadecylimidazoline magnesium. nitrate, di(heptadecylimidazoline acetic acid) zinc chloride, diheptadecylimidazoline zinc acetate, di- (heptadecylimidazoline acetic acid) cadmium sulfate, di(heptadecylimidazoline acetic. acid) cadmium nitrate, di(heptadecylimidazoline acetic acid) cadmium chloride, di(heptadecylimidazoline acetic acid) mercury sulfate, di(heptadecylimidazoline acetic acid) mercury acetate and di(heptadecylimidazoline acetic acid)me rc ury bromide.

Illustrative of a VI of the periodic table.

2,881,177 Patented Apr. 7, 1:959

The compositions of my invention also include the chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group III of the periodic table; Illustrative of such chelates are: triheptadecylimidazoline aluminum sulfate, triheptadecylimidazoline aluminum nitrate and triheptadecylimidazoline aluminum chloride.

My compositions also include chelates formed by reacting acid salts of 2-heptadecylimidazoline with the. salts of the metals of group III of the periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) aluminum sulfate, tri(heptadecylimidazoline acetic acid) aluminum nitrate and tri(heptadecylimidazoline acetic acid) aluminum chloride.

The compositions of my invention also include .the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of group IV of the periodic table, Illustrative of such chelates is diheptadecylimidazoline lead nitrate.

Still other compositions within the scope of my in-. vention are the chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group IV of the periodic table. Illustrative of such chelates is di(heptadecylimidazoline acetic acid) lead nitrate. i o

Other compositions within the scope of my invention are the chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group VI of the periodic table. Illustrative of such chelates are: trihept a decylimidazoline chromium sulfate, triheptadecylimidazoline chromium nitrate and triheptadecylimidazoline chromium chloride.

Still other compositions of my invention are the chelates formed by reacting the acid salts of'2'-heptadecylimidazoline with the salts of the metals of group Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) chromium sulfate, tri(heptadecylimidazoline acetic acid) chromium nitrate and tri(heptadecylimidazoline acetic acid) chromium chloride.

Other compositions within the scope of my invention are the chelates formed by reacting 2-heptadecylimidaz-' oline with the salts of the metals of group VII of the periodic table. Illustrative of such chelates are: diheptadecylimidazoline manganese nitrate, diheptadecylimidaza oline manganese chloride and diheptadecylimidazoline manganese sulfate.

The compositions of my invention also include chelates formed by reacting the acid salts of Z-heptadecylimidaz-v oline with the salts of the metals of group VII of the periodic table. Illustrative of such chelates are: di(heptadecylimidazoline acetic acid) manganese nitrate, di-. (heptadecylimidazoline acetic acid) manganese chloride and di(heptadecylimidazoline acetic acid) manganese sulfate. 7

Another group of compositions within the scope of my invention are the chelates formed by reacting 2-heptadecylimidazoline with the salts of the metals of group VIII of the periodic table. Illustrative of such chelates are: triheptadecylimidazoline iron sulfate, triheptadecylimidazoline iron phosphate, triheptadecylimidazoline iron nitrate, triheptadecylimidazoline cobalt sulfate and diheptadecylimidazoline nickel nitrate. P

Still another group of compositions within the, scope of my invention are the chelates formed by reacting the acid salts of Z-heptadecylimidazoline with the salts of the metals of group VIII of the periodic table. Illustrative of such chelates are: tri(heptadecylimidazoline acetic acid) iron sulfate, tri(heptadecylimidazoline acetic acid) iron phosphate, tri(heptadecylimidazoline acetic. acid) iron nitrate, tri(heptadecylimidazoline acetic acid) cobalt sulfate and di(heptadecylimidazoline acetic acid) nickel nitrate.

Other compositions within the scope of my invention are the chelates formed by reacting Z-heptadecylimidazoline with the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri(heptadecylimidazoline) cerium acid sulfate.

Still other compositions Within the scope of my invention are'the chelates formed by reacting the acid salts of Lheptadec-ylimidazoline with the salts of the metals of the lanthanum series of the periodic table. Illustrative of such chelates is tri(heptadecylimidazoline acetic acid) cerium acid sulfate.

The compounds of the present invention can be prepared by a process which comprises bringing a 2-heptadecylimidazoline into reactive admixture with a metal salt under conditions to produce a chelate.

The metal salts which are best suited for use in this invention are water-soluble. For this reason, the reaction should be conducted in a solvent medium which comprises at least 80 percent water. Other solvents which can be used together with water are methanol, ethanol, isopropanol and pyridine. The two reactants, namely the 2-heptadecylimidazoline and the metal salt, need not be added to the solvent in any particular order. Preferably, however, in the case of Z-heptadecylimidazoline, the metal salt is dissolved in water and the Z-hepta- N The reaction is preferably conducted at 20 to 30 C.

but can be conducted at temperatures between about 0 C. and about 80" C.

The following examples are illustrative:

EXAMPLE I DKLhe'ptaGeeyIimidaZoline acetic acid) magnesium II sulfate (C 4H O N SMg) was prepared as follows:

About "19.4 grams of magnesium sulfate hydrate (MgSO -7H O) were dissolved in 3000 milliliters of'water and the solution was agitated at a slow rate. To this solution was added, dropwise over a period of 15 minutes, 100 milliliters of an isopropanol solution containing 29 grams of dissolved acetic acid salt of Z-heptadecylimidazoline. An immediate precipitate formed, which was filtered at reduced pressure in a large Biichner funnel. The precipitate was washed twice with water and vacuum-dried at 50' C. and mm. Hg for about 24 hours. The dried precipitate which was a light cream color, had a melting point of 130-150 C. The calculated percentage composition for a 100' percent pure compound and the actual composition (by weight) found for the magnesium II chelate prepared as described above are compared in Tablel. In Table I, R is 2-heptadecylimidazolineacetic Table I PERCENTAGE COMPOSITION OF DI(2-HEPTADEOYLIM- 'IDAZOLINE AOETIG ACID) MAGNESIUM II SULFATE The dataobtainedngree satisfactorily-withrthe theoretiietructure' ot the magnesium chelate containing 2 moles of 2'-heptadecylimidazoline acetic acid per mole of magnesium, in accordance with the accepted coordin'ant num" "ber cs4 for My.

f4 EXAMPLE II Di(2-heptadecylimidazoline acetic acid) magnesium II nitrate (C H O N Mg) was prepared using the same procedure as in Example I, except that 20.4 grams of magnesium nitrate hydrate (Mg(No .6H,O) were employed in place of the 19.4 grams of magnesium sulfate hydrate. The dried precipitate which was formed had a melting point of 8446' C. The calculated percentage composition for a percent pure compound and the actual composition (by weight) found for the magnesium II chelate prepared as described above are compared in Table II. In Table .II .R is Z-heptadecylimidazoline acetic acid. Table II PERCENTAGE eourosi'wios o'F btt'z-finp'mnacnm- IDAZOLINE ACE'IIO ACID) MAGNESIUM n NITRATE ,pflalculafibdr i ,Percent Oom- Foundd Per- Element pc on cent em- 1 position 63.6 ii sli The data obtained agree satisfactorily with thetheoretical structure of the magnesium chelate containing 2 moles of 2 heptadecylimidazoline 'acetica'cidper' mole of magnesium, in accordance with the accepted coordinate number of 4 for Mg.

EXAMPLE III Di(2-heptadecylimidazoline acetic acid) zinc II chloride (c H,,0,N,c1,zn was prepared using the same procedure as in Example I, except that 10.8 grams of zinc chloride (ZnCl,) were used in place of the 19.4 grams of magnesium sulfate hydrate. The dried precipitate which was formed had a melting pdint of 84-86 C. The calculated percent pure compound and the actual composition (by weight) found for the zinc II cheiate prepared as described above are compared in Table 'III. In Table III, R is 2-heptadecylimidazoline acetic acid.

Table-III PERCENTAGE COMPOSITION or mu-nnrrrannovnm- IDAZOLINE nonrrro aom) ,ZINC II :onnonmn a e 1 a, eroen 0 Element Oompol'ttion 2R to 1 Composition ZnCl: 1

a a 0 I 713' at: N H 0.4 1.4 zn 7.:5. as 01...... 8.1 8.2

The data obtained agree satisfactorily with the theoretical structure of the zinc chelate containingZmoles-of 2-zheptadecylimidazoline :acetic acid per ,mole of zinc, .in accordance withqthe accepted coordinate number cf'kfor 5 Table IV PERCENTAGE COMPOSITION or nuanni 'ran'noynm- IDAZOLINE ACETIC ACID) ZINC n m'raa'rn Calculated,

Percent Found, Element Composition Percent 2R to 1 Zn Composition C 57.0 57. 4 F 9. 6 11.4 0 17. 3 11. 0 N 9. 1 8. 6 Zn 7. 1 4. 4

The data obtained agree satisfactorily with the theoretical structure of the zinc chelate containing 2 moles of 2-heptadecylimidazoline acetic acid per mole of zinc, in accordance with the accepted coordinate number of 4 for Zn++.

. EXAMPLE V Di(2-heptadecylimidazoline acetic acid) cadmium II chloride (C H 0 'N Cl Cd) was prepared using the same procedure as in Example I, except that 27.3 grams of cadmium chloride hydrate '(CdCl .2.SH O) were used in place of the 19.4 gramsfo'fmagnesium sulfate hydrate.

'The dried precipitate which-was formed had a melting point of 667 0 C. Th'ecalculated percent pure compound and the actual composition (by weight) found for the cadmium II chelate prepared as described above are "compared in Table V. In Table V, R is Z-heptadecylimidazoline acetic acid.

Table V PERCENTAGE COMPOSITION .OF- DI(2-HEPTADECYLIM- IDAZOLINE ACETIC ACID) CADMIUM II CHLORIDE Calculated, Found,

Percent Percent Element Composition Composition 2R to 1 CaCla C 57. 4 56. 4 H 9. 6 10. 6 O 7. 0 6. 8 N 6. 1 6. 6 Cd 12. 2 11. 4 Cl 7. 7 11.

The data obtained agree satisfactorily with the theoretical structure of the cadmium II chelate containing 2 moles of 2-heptadecylimidazoline acetic acid per mole of cadmium, in accordance with the accepted coordinate number of 4 for Cd. 1

EXAMPLE VI Table VI PERCENTAGE COMPOSITION OF DI(2-HEPTADECYLIM- IDAZOLINE ACETIC ACID) MERCURY II SULFATE Calculated,

Percent Found, Element Composition Percent 2R to 1 Composition HgSOa 6 I The-"data obtained agree satisfactorily witii the theoretical structure of the mercury II chelatecontaining '2 moles of Z-heptadecylimidazoline acetic acid per mole of mercury, in accordance with the accepted coordinate number of 4 for Hg.

EXAMPLE VII --Di(Z-heptadecylimidazoline) zinc II chloride was prepared using the same procedure as in Example I, except that 30 grams of Z-heptadecylimidazoline were used in place of the 29 grams of 2-heptadecylimidazoline acetic acid and 13.3 grams of anhydrous zinc chloride (ZnCl were used in place of the 19.4 grams of mag- .nesium sulfate hydrate. The dried precipitate-which was .formed had a melting point of 127-129 C. The calculated percent pure compound and the actual composition (by weight) found for the zinc II chelate prepared as described above are compared in Table VII. In Table VII, R is Z-heptadecylimidazoline. 1

Table VII PERCENTAGE COMPOSITION OF DI(2-HEPTADECYLIM- IDAZOLINE) ZINC II CHLORIDE Calculated,

Percent Found, Element Composition Percent 2R to 1 Composition ZnCl:

C 63.8 63.1 10.7 11.0 0 N 7.4 7.9 Zn 8.7 8.7 Cl 9.4 t 9.7

The data obtained agree satisfactorily with the theoretical structure of the zinc II chelate'c'ontaining' 2 moles of Z-heptadecylimidazoline per mole of zinc, in accordance with the accepted coordinate number of for Zn++.

EXAMPLE VIII Di(khcptadecylimidaaoline) zinc II acetate u as a s I I was prepared using the same procedure as in Example I,

except that 30 grams of 2-heptadecylimidazo1ine were used ,in place of the 29 grams of 2-heptadecy1imidazoline acetic acid and 21.4 grams of 'zinc acetate hydrate were used in place of the 19.4 grams of magnesium sulfate hydrate. The dried precipitate which was formed had a melting point of l01l03 C. The calculated percent pure compound and the actual composition (by weight) found for the zinc II chelate prepared as described above are compared in Table VIII. In Table VIII, R is Z-heptadecylimidazoline.

PERCENTAGE COMPOSITION OF DI(2-HEPTADECYI1IM IDAZOLINE) ZINC II ACETATE Calculated, Found, Element Percent Com- Percent position 28. to Composition 1 Zn (CaHaOrh The data obtained agree satisfactorily with the theoretical structure of the zinc II chelate containing 2 moles of 2-heptadecylimidazoline per mole of zinc, in accordance with the accepted coordinate number of 4 for Zn++.

The other chelates of this invention can be prepared in a similar manner.

Table VIII I sesame? this "invention. :are, \useful ias. fungicides. JRepresentative 'chelates; contemplatediherein were tested for fungicidal activity by means of the slide germination-test. 'SEssentially this test method consisted of germinating spores in continual contact, on glass sli'desywith given concentrations of the chemical runder -test. 'l'he germinationwas-observed after 24 hours andtheamount of the chemical needed to inhibit germination 6f '50 percent (LB. 50 value) of the -"spores *wasmle'termined. The procedure =used is more' 'fullysetforth in a paper entitled The Slide- Germination *Method of Evaluating Protectant Fungicides, published in -iPhytopathol gy, July 1943; vol. 'XXXIIL'NQ. 7,; pp. 627-632. "Two ditferent'andtypical "fungi were 'usd 'f0rfthiste'st. The fun'gi tested were Sclefatinia fruclicola (WintDIRehm (St) and *A lteniaria oler' aede" (i420. The values-"in" Table IX below represent tlie partsby' weight 'ofthe 'ch'elate under test, :in 'a "millionpartfbw'weight of'liquidflto prevent the'igem'lination of 50 percent of the"spores. Theliquid used, which of itself did not inhibit 'germination of the spores, was .Lins solution, :which consists of .10 grams .ofv dextrose, 2.46 grams ofvMgSQ -7H@O;aud100 mL 'ofidistilled water. Ten milliliters of thissolution were added to --each 1-00 milliliters of spore.

The periodicnable "referred to i in this application is the periodic "table of "the ""elernents revised 'inacc'ordance with the Journal "of the *American Chemical "Society, volume 76, page 2033 (.1954).

This application is a continuation-in-part of my co- ;pendingapplication,Serial No. 545,108, filed November 4, 1955, nowPatentNo. 2,789,115.

I claim:

.1. A chelate having the structural formula MR whereinf- Rt-is amemberiselected from the-group consisting of 2-heptadecylimidazoline and acid salts thereof, M is both the anion and cation of an inorganic salt of a metal of group II of the periodic table and n is an integer having a value of one-halfthe coordination number of said metal.

2. A chelate having the structural formula MR where- .in R is 2-heptadecylimidazoline M is both the anion and cation or an inorganic salt of a metal of Group II of the periodic table'and n' isan integer having a value of Onehalf the coordination numb'er of said metal.

3. A-chelate having the structuralformula MR wherein R is an acid salt of Z-heptadecylimidazoline, 'M isboth the anion and cation of an inorganic salt of a metal of gronp:II- of theiperiodic table and 'n is an integer having a value of one-half .the coordination number of said :metal.

4. .-A chelate having thestructural. formula MR whereinR is 2'heptadecylimidazoline acetic acid, M is both the anionland cation-of an inorganic salt of a metal of group 'II of theperiodic tableand-n is an integer having a value of one-half the coordinationnumber of said metal.

.5. Di(2eheptadecylimidazoline.acetic acid) zinc sulfate.

.6. Di(Z-heptadecylimidazoline acetic acid) cadmium sulfate.

7. Di(2-heptadecylimidaz oline acetic acid) mercuric sulfate.

'8..Di(2sheptadecylimidazoline acetic acid) magnesium .-nitrate.

.9..;Di(2+heptadecylimidazoline acetic acid) magnesium chloride.

References- Citedinthe file of 7 this patent *UNITEDSTATES PATENTS OTHER REFERENCES Klingenstein: Ber. Deut. Chem vol. 28, pp. 1175-76 (1395). 

1. A CHELATE HAVING THE STRUCTURAL FORMULA MRN WHEREIN R IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF 2-HEPTADECYLIMIDAZOLINE AND ACID SALTS THEREOF, M IS BOTH THE ANION AND CATION F AN INORGANIC SALT OF A METAL OF GROUP 11 OF THE PERIODIC TABLE AND N IS AN INTEGER HAVING A VALUE OF ONE-HALF THE COORDINATION NUMBER OF SAID METAL. 